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Guest-dependent bond flexibility in UiO-66, a "stable" MOF.

Kevin Fabrizio1, Anastasia B Andreeva1, Kentaro Kadota1

  • 1Department of Chemistry and Biochemistry, Material Science Institute, University of Oregon, Eugene, OR 97403, USA. cbrozek@uoregon.edu.

Chemical Communications (Cambridge, England)
|January 13, 2023
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Summary

We introduce "flexibility constants" to quantify the stability of the robust metal-organic framework UiO-66. This study reveals that guest molecules promote the reversible breaking of metal-linker bonds within the framework.

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Area of Science:

  • Materials Science
  • Chemistry
  • Physical Chemistry

Background:

  • Metal-organic frameworks (MOFs) are advanced porous materials with high surface areas.
  • UiO-66 is a benchmark MOF known for its exceptional thermal and chemical stability.
  • Understanding MOF stability under various conditions is crucial for their practical applications.

Purpose of the Study:

  • To quantify the flexibility and bond dissociation characteristics of UiO-66.
  • To investigate the influence of temperature and guest molecules on MOF stability.
  • To establish a thermodynamic basis for MOF bond reversibility.

Main Methods:

  • Introduction of
  • flexibility constants
  • as a measure analogous to metal-ligand stability constants.
  • Experimental studies across a wide temperature range.
  • Experiments conducted in both vacuum and the presence of guest solvents.

Main Results:

  • UiO-66 exhibits measurable flexibility constants.
  • Thermodynamic parameters governing metal-linker bond equilibrium were extracted.
  • Guest molecules were found to significantly promote the reversible dissociation of MOF metal-linker bonds.

Conclusions:

  • The concept of flexibility constants provides a new metric for MOF stability.
  • UiO-66's stability is influenced by temperature and the presence of guest molecules.
  • Guest molecules play a critical role in the reversible bond dynamics of MOFs, impacting their structural integrity.